Chromiferous azo-dyestuffs



United States Patent CHROMIFEROUS AZO-DYESTUFFS Arthur Buehler, Rheinfelden, Alfred Fasciati, Bottmiugen, and Christian Zickendraht, Binningen, Switzerland, assignors to Ciba Limited, Basel, Switzerland, a SWISS firm No Drawing. Application December 15, 1952, Serial No. 326,141

Claims priority, application Switzerland December 15, 1951 Claims. (Cl. 260-147) According to this invention valuable new chromiferous azo-dyestutfs are made by treating with an agent yielding chromium a monoazo-dyestutf which is freefrom sulfonic acid and carboxylic acid groups and corresponds to the general formula in which R1 represents a benzene radical bound to the azo linkage in ortho-position to the hydroxyl group, R2 represents the radical of a keto-rnethylene compound bound to the 2120 linkage in a position vicinal to the keto group, and X represents an aryl radical which contains a substituent of the formula in which Z1 and Z2 each represent a hydrogen atom or alkyl or hydroxyalkyl radical containing at most 6 carbon atoms.

The monoazo-dyestufls corresponding to the above formula, and used as starting materials in the present process, can be made by coupling a keto-methylene com pound capable of coupling in a position vicinal to a keto group and free from sulfonic acid and carboxylic acid groups with an ortho-hydroxy-diazo-compound free from sulfonic acid and carboxylic acid groups and obtained by diazotizing an amine of the formula in which R1 and X have the meanings given above.

The benzene radical of those 2-amino-1-hydroxybenzenes may be bound in the 4-, 5- or 6-position to the SO2-NH-X group, and it may contain further substituents incapable of salt formation, for example, a halogen atom or a nitro group. The aryl radical X may be, for example, a naphthalene or advantageously a benzene radical, which contains a sulfonic acid amide group, advantageously one of the formula SO2-NH2 and, if desired, further substituents such as an alkyl group (for example, methyl), a chlorine atom or the like.

Compounds of the Formula 2 can be prepared, for example, by reacting an amine of the formula XNH2,

in which X has the meaning given above, with l-chloro- Z-nitrobenzene-4-sulfonic acid chloride, reacting the resulting 1-chloro-2-nitro-benzene-4-sulfonic acid amide with an alkali or alkaline earth metal hydroxide to form the corresponding l-hydroxy-compound, and converting the ice nitro-group in the latter compound in known manner into an amino group. Instead of using l-chloro-Z-nitro-ben zene-4-sulfonic acid chloride as starting material there may be used, for example, 1:Z-benzoxazolone-S-sulfonie acid chloride, in which case, after the condensation with the amine of the formula X-NH2 to form the corresponding 1:2-benzoxazolone-S-sulfonic acid amide, it is only necessary to hydrolyze the oxazolone ring in order to obtain the compound of the formula 2.

As amines of the Formula 2 there may be mentionedl 2-amino 1-hydroxybenzene-4-sulfonic acid-N- 1 -naphthyl'- amide-4'-sulfonic acid amide, 2-amino-l-hydroxy-6-chlorobenzene-4-sulfonic acid phenylamide-3-sulfonic acid amide, Z-amino-1-hydroxy-6-nitrobenzene-4-sulfonic acidphenylamide-4-sulfonic acid amide, 2-amino-1-hydroxy'- 4-nitroor -4-chlorobenzene-6-sulfonic acid phenylamide- 3-sulfonic acid amide, Z-amino-1-hydroxybenzene-4- or -5-sulfonic acid phenylamide 3' sulfonic acid-methylamide, Zamino-l-hydroxybenzene-4- or -5-sulfonic acidphenylamide 3' sulfonic acid hydroxyethylamide, 2- amino-l-hy'droxybenzenelor -5-sulfonic acid-phenyL amide-4'-sulfonic acid-isopropylor -n-butylamide, 2- amin-o-1-hydroxy-4-chlorobenzene-S-sulfonic acid phenylamide-3'-sulfonic acid amide and especially 2-amino-lhydroxybenzene-4- or -5-sulfonic acid phenylamide-2, -3'- or -4-sulfonic acid amide.

There come into consideration as coupling components for preparing the monoaz'o-dyestufi's serving as starting materials in the present process keto-methylene compounds which are free from sulfonic acid and carboxylic acid groups and are capable of coupling in a position vicinal to the keto group. As compounds of this kind there are to be understood, for example, those which contain the keto-methylene group responsible for coupling in an open chain or advantageously those which contain the keto-methylene group in a heterocyclic ring, and above all a pyrazolone ring.

As compounds of this kind there may be mentioned: Acylacetic acid esters or amides, such as acetoacctic acid amide, acetoacetic acid methylamide, n-butylamide or phenylamide, acetoacetic acid dimethylamide, acetoacetic acid 2 or 3- or 4'-chlorophenylamide, benzoylacetic acid amide, benzoy'lacetic acid phenylamide, and also barbituric acid and 2:4-dihydroxy-quinoline. However, especially valuable starting materials are pyrazolones, such as S-methylor 3-phenyl-5-pyrazolone, 1- n-butyl-3-methyl-5-pyrazolone, l-phenyl-3-methyl-5pyrazolone, 1-(2- or 3- or 4'-chlorophenyl)-3-methyl- 5-pyrazolone, 5-pyrazolone-3-carboxylic acid amide, 5- pyrazolone-3-carboxylic acid methyl, -ethyl-, isopropylor -nbutylamide, 5-pyrazolone-3-carboxylic acid-2'-, -3'- or 4'-chlorophenylamide, 5-p-yrazolone-3-carboxylic acidphenylor -3-methyl-phenyl-amide, l-phenyl-S- pyrazolone-3-carboxylic acid amide, l-phenyl-S-pyrazo- .lone-3-carboxylic aci'd-2'-, -3- or -4-chlorophenylamide, 1-phenyl-5-pyrazolone-3-carboxylic acid methyl-, -isopropylor phenylamide.

The amines of the Formula 1 can be diazotized in the usual manner, for example, with the use of sodium nitrite and hydrochloric acid. The coupling of the resulting diazo-compounds with the aforesaid coupling components can also be carried out in the usual manner.

After the coupling reaction is finished the dyestuffs can easily be separated from the coupling mixture by filtration, as they are generally only slightly soluble in water. In fact in the form of their alkali compounds they are still soluble in water to such an extent that they can be used for [dyeing from dyebaths requiring no addition of acid, and are therefore especially suit- L. able for "dyeing' by the single bath chroming process, lt h in some s s th y ve. go r sult iusiy n by the after-chroming process.

In the present process there may be obtained chromium compounds that contain 1 atom of chromium bound in complex union with one or two molecules of monoazodyestuff. In order to obtain the easily prepared and valuable. 1:2,-type ofchromium compounds it ,isggenerally desirable to carryout the treatment with the agent yielding chromium by using a quantity of an agent yielding chromium corresponding to about one atomic proportion of chromium for every two molecular proportions of a dyestuif of the general Formula 1 or for every ojne molecular proportion of each of two different dyestuffs, at least one of which corresponds to the general Formula 1; and/or by carrying out the chroming treatment in a weakly acid to alkalinemedium. Consequently, there are especially suitable for carrying out the process chromium compounds that are stable in alkaline media such, for example, as chromium compounds of aliphatic or aromatic ortho-hydroxy-carboxylic ,acids which contain chromium in complex union. As exain ls f. a t c, yd o b x ci th m y be mentioned, inter alia, lactic acid, glycollic acid, citric acid and especially tartaric acid; among the aromatic ortho-hydroxycarboxylic acids there may be mentioned those of the benzeneseries such as 4-, 5- or G-methyll-hydroxybenzene-2-carboxylic acid and above all 1- hydroxybenzeneQ-carboxylic acid itself. The conversion of the dyestufis into the complex chromium compounds is carried out with advantage with the application of heat, under atmospheric or superatmospheric pressure, for example, at the boiling temperature of the reaction mixture, i f desired, in the presence of suitable additions, for example, salts of organic acids, bases, organic solvents or other agents assisting the formation of complexes. The above described chroming treatment may be applied, f or' example, to a single 'dyestufi of the Formula 1.1, It is also possible, and is in many cases of advantage, for example, for. producing various tints, to subject to theichroming treatment .ina corresponding manner a mixture .oftwo different dyestuifs of the Formula 1, or a mixture of. one dyestufi- 3 of that formula and another ortho:ortho-dihydroxymonoazo-dyestuif nee from sul-' tonic/acid and carboxylic acid groups. 1 Thelchromiurn' compounds 'so obtained contain two molecules of monoazo-dyestuff bound in complex union to one atom of. chromium, and at least one of the monoafzca'dyes tuif molecules must correspond to the general greases pounds of'tbis kind, which contain two molecules of the saiagd s tufio th lioxm laL,

The new chromium compounds are soluble in water and in weakly acid media, and are indeed more soluble than the initial 'dyestufis used for making them. They are suitable for dyeing a very wide variety of substances, such as plastic masses, resins, lacquers and the like, but especially for dyeing or printing animal materials such as silk, leather and especially wool, and also synthetic materials composed of superpolyamides or superpolyurethanes. They ar'e'suitable above all for dyeing from weakly alkaline, neutral or weakly acid, for example, acetic acid, baths. The dyeings so produced are distinguished by their good level character, good properties of wet fastnes's and very good fasteness to light.

The following examples illustrate the invention, the parts and percentages being by weight:

Example 1 34.3 parts of 2-amino-1-hydroxybenzene-4-sulfonic acid anilide-3'-sulfonic acid amide are dissolved in 200 parts of 1 N-hydrochloric' acid at 40 C.' The mixture is cooled to 0 C. by the addition of ice and diazotization is brought about at..0-10 C; with 25 parts of a4 N-solution of sodium nitrate. The resulting yellow diazo-suspension is neutralized with sodium carbonate, and then coupled with a solution, cooled to about 5 C., of 17.8 parts of l-phenyl-3-methyl-5-pyrazolone in parts of water, 4.2 parts of sodium hydroxide and 5 parts of sodium carbonate. When the coupling is finished the precipitated dyestutf is filtered 01f, washed with sodium chloride solution of 2 percent strength and dried.

j5.28 parts of the dyestuif so obtained are dissolved in parts of water and 5 parts by volume of a 2 N-solution of sodium hydroxide at the boiling temperature, then mixed with l5 parts of a solution of sodium chromosalicylate containing 2.6 percent of chromium, and the mixture is boiled for about 3 hours under reflux. The chomium compound is precipitated by neutralizing the chroming mixture with dilute acetic acid and salting out. The filtered off and drieddyestuff dissolves in hot water and in dilute sodium carbonate solution with an orange coloration, and dyes wool from a neutral or weakly acid bath orange tints which arefast. to light.

In the following table are given the properties of further chromium complexes obtainableinan analogous manner. In column III is given the tint of the dyeing obtainable on wool or fibers of a superpolyamide with the chromium complex of the dyestuff obtained from the components Formula'l. J- Especially valuable are chromium com- 50 given in columns I and H..

1 II L1 III main-Component Coupling Component on I o cHPo'o-onFb-HN- 1...... reddish yellow.

. 'L. 1 I 2...... CHwco-CHEa-HN no.v

agreemer V II III Blaze-Component I v Coupling Component OH CH;

1 NH 2N- D H26 .I I n s oiNm oo-N- EiOiNHQ c1 )3 (3H3 C=N 11..-.. NH: D0.

,c -N-Q soimz -SO2NH2 21 NH 2N D 12.-- o. H20 1 OON SO;NH-CH3 )11 OH; 13..... NH 2 Do.

l SO2-NH The Z-amino-l-hydroxybenzene-4 sulfonic acid-phenyl- Example 3 amide-3-sulfonic acid amide used as diazo component in this example can be made by reacting l-chloro-2 nitrobenzene-4-sulfonic acid chloride with l-aminooenzene-B-sulfonic acid amide, exchanging the chlorine atom in the resulting l-cl1loro-2-nitrohenzeno/issulfonic acid phenylamide-3'-sulfonic acid amide for a hydroxyl group by means of an alkali or alkaline earth metal hydroxide, and finally reducing the nitro group in known manner to an amino group.

The Z-amino-l-hydroxybenzene-5-sulfonic acid-phenyl amide-3'-sulfonic acid amide can he made by reacting 1:2-benzoXazolone-5-sulfonic acid chloride with l-aminobenzene-3-sulfonic acid amide, and splitting up the mo azolone ring in the resulting .l22-henzo2gazolone-5eulfonic acid-phenylamide-3-sulfonic acid amide, for example, by means of an alkali hydroxide.

Example 2 5.28 parts of the dyestuif obtained as described in the first paragraph of Example 1 and 5.91 parts of the dyestufi obtained from diazotized Z-amino-l-hydroxybcnzene-4- sulfonic acid phenylamide-3'-sulfonic acid amide and 5- pyrazolone-S-cflrboxylic acid para-chloro-phenylamide are dissolved in 240 parts of waterand parts by volume of a 2 N-solution of sodium hydroxide at the boiling temperature, parts of a solution of sodium chrome-- salicylate containing 2.6 percent of chromium are then added, and the mixture is boiled under reflux for about 3 hours. By neutralizing the chroming mixture with dilute acetic acid and salting out the chromium compound is precipitated. The filtered ed and dried mixed chromium complex dyes wool from a neutral to weakly acid bath red tints which are fast to washing.

2 parts of the chromiferous dyestuff obtainable as described in Example 1 are dissolved in 4000 parts of water, 10 parts of crystalline sodium sulfate are added, and 100 parts of well wetted WOO'l are entered at 40-50 C. into the dyebath so prepared. There are then added 2 parts of acetic acid of 40 percent strength, the temperature is raised to the boil in the course of /2 hour and dyeing is carried on at the boil for hour. The wool is finally rinsed in cold Water and dried. The wool is dyed an orange tint which is fast to washing and has a good fastness to light. p

The same dyeing is obtained by dyeing from a neutral hath, that is to say, w to the bath.

What is claimed is:

l. A complex chromium compound containing one atom of chromium bound in complex union with substantially two monoazo dyestuif molecules free from sulfonic acid and carboxylic' acid groups and of which at least one corresponds to the formula 1 ithout the addition of acetic acid two molecules of monoazo-dyestuffs free from sulfonic two monoazo dyestufi molecules both of which correspond acid and carboxylic acid groups and corresponding to the to the formula formula N=NPz I C=N 41H:

10 (PB-N11 SOPNH- S OsNH-C yr-lHIn-l s ONH2 wherein Pz represents a 5-pyrazolone radical bound t 1 t gompl P p g g fi the azo linkage in 4-position and n represents a whole a om o c rommm m comp ex W1 su S an m y number up to two monoazo dyestulf molecules both of which correspond 3. A complex chromium compound containing one to the formula atom of chromium in complex union with substantially OH HO two molecules of monoazo-dyestuffs free from sulfom'c 2o acid and carboxylic acid groups and corresponding to the formula :1

C=N OH H? JJH O-N-R| I OPNH C=N IJH' somm 2 11 30 References Cited in the file of this patent UNITED STATES PATENTS 2,495,244 Felix et al. Ian. 24, 1950 wherein R3 represents a benzene radical. 2,572,394 Ruckstuhl et a1. Oct. 23, 1951 4. The complex chromium compound containing one 2,597,676 Schetty May 20, 1952 atom of chromium in complex union with substantially 35 2,634,263 Steinemann Apr. 7, 1953 

1. A COMPLEX CHROMIUM COMPOUND CONTAINING ONE ATOM OF CHROMIUM BOUND IN COMPLEX UNION WITH SUBSTANTIALLY TWO MONOAZO DYESTUFF MOLECULES FREE FROM SULFONIC ACID AND CARBOXYLIC ACID GROUPS AND OF WHICH AT LEAST ONE CORRESPONDS TO THE FORMULA 